In organic chemistry, a pericyclic reaction is a type of organic reaction wherein the transition state of the molecule has a cyclic geometry, and the reaction progresses in a concerted fashion. Pericyclic reactions are usually rearrangement reactions. The major classes of pericyclic reactions are:
| Name | Bond changes | |
|---|---|---|
| Sigma | Pi | |
| Electrocyclic reaction | + 1 | -1 |
| Cycloaddition | +2 | -2 |
| Sigmatropic reaction | 0 | 0 |
| Group transfer reaction | + 1 | -1 |
| Cheletropic reaction | + 2 | - 2 |
| Dyotropic reaction | 0 | 0 |
In general, these are considered to be equilibrium processes, although it is possible to push the reaction in one direction by designing a reaction by which the product is at a significantly lower energy level; this is due to a unimolecular interpretation of Le Chatelier's principle. Pericyclic reactions often have related stepwise radical processes associated with them. Some pericyclic reactions, such as the [2+2] cycloaddition, are 'controversial' because their mechanism is not definitively known to be concerted (or may depend on the reactive system). Pericyclic reactions also often have metal-catalyzed analogs, although usually these are also not technically pericyclic, since they proceed via metal-stabilized intermediates, and therefore are not concerted.
A large photoinduced hydrogen sigmatropic shift was utilized in a corrin synthesis performed by Albert Eschenmoser containing a 16π system.[1]
Due to the principle of microscopic reversibility, there is a parallel set of "retro" pericyclic reactions, which perform the reverse reaction.
Pericyclic reactions also occur in several biological processes.